1-((4R,5R)-5-((1-tert-butyl-1,1-dimethylsilyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)propan-2-one | 872831-95-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-((4R,5R)-5-((1-tert-butyl-1,1-dimethylsilyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)propan-2-one
• 英文别名: 1-[(4R,5R)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-1,3-dioxolan-4-yl]propan-2-one
• CAS: 872831-95-3
• 化学式: C₁₅H₃₀O₄Si
• 分子量: 302.486
• InChiKey: ISUXVCQJXSRCST-CHWSQXEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-((4R,5R)-5-((1-tert-butyl-1,1-dimethylsilyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)propan-2-one 在 二氯双(三邻甲苯膦)合钯(II) 、 三正丁基氟化锡 、 三乙胺 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 4.0h， 生成 tert-butyl N-(2-(benzyloxy)ethyl)-N-((6-[3-((4R,5R)-5-((1-tert-butyl-1,1-dimethylsilyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-ylmethyl)-2-oxopropyl]-1,3-benzodioxol-5-yl)methyl) carbamate
  参考文献：
  名称：

  Asymmetric Total Synthesis of the 1-epi-Aglycon of the Cripowellins A and B

  摘要：

  [GRAPHICS]The unusual [5.3.2]-bicyclic structure of the insecticidal Amaryllidaceae alkaloids cripowellin A (1) and B (2) has been synthesized for the first time via a sequence of Sharpless dihydroxylation, ring-closing metathesis, and intramolecular Heck reaction. The asymmetric synthesis of the 1-epiaglycon 82 proceeds with virtually complete diastereo- and enantioselectivity (de, ee >= 98%) in 13 steps and an overall yield of 5.6%. In addition, three alternative approaches toward the aglycon 3 are also described focusing on (1) the alkylation of the 2-benzazepinedithianes 35 and 36 with the electrophile 11, (2) a radical cyclization of the precursor (R/S,S,S)-39, and (3) an intramolecular arylation reaction of the aryl ketone 47.

  DOI：

  10.1021/jo0518093
• 作为产物：
  描述：

  (-)-2,3-O-亚异丙基-D-苏力糖醇 在 咪唑 、 正丁基锂 、 碘 、 sodium hydride 、 silver nitrate 、 二异丙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 正己烷 、 水 、 甲苯 为溶剂， 反应 1.58h， 生成 1-((4R,5R)-5-((1-tert-butyl-1,1-dimethylsilyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)propan-2-one
  参考文献：
  名称：

  Asymmetric Total Synthesis of the 1-epi-Aglycon of the Cripowellins A and B

  摘要：

  [GRAPHICS]The unusual [5.3.2]-bicyclic structure of the insecticidal Amaryllidaceae alkaloids cripowellin A (1) and B (2) has been synthesized for the first time via a sequence of Sharpless dihydroxylation, ring-closing metathesis, and intramolecular Heck reaction. The asymmetric synthesis of the 1-epiaglycon 82 proceeds with virtually complete diastereo- and enantioselectivity (de, ee >= 98%) in 13 steps and an overall yield of 5.6%. In addition, three alternative approaches toward the aglycon 3 are also described focusing on (1) the alkylation of the 2-benzazepinedithianes 35 and 36 with the electrophile 11, (2) a radical cyclization of the precursor (R/S,S,S)-39, and (3) an intramolecular arylation reaction of the aryl ketone 47.

  DOI：

  10.1021/jo0518093

文献信息

• Asymmetric Total Synthesis of the 1-<i>e</i><i>pi</i>-Aglycon of the Cripowellins A and B
  作者：Dieter Enders、Achim Lenzen、Michael Backes、Carsten Janeck、Kelly Catlin、Marie-Isabelle Lannou、Jan Runsink、Gerhard Raabe

  DOI：10.1021/jo0518093

  日期：2005.12.1

  [GRAPHICS]The unusual [5.3.2]-bicyclic structure of the insecticidal Amaryllidaceae alkaloids cripowellin A (1) and B (2) has been synthesized for the first time via a sequence of Sharpless dihydroxylation, ring-closing metathesis, and intramolecular Heck reaction. The asymmetric synthesis of the 1-epiaglycon 82 proceeds with virtually complete diastereo- and enantioselectivity (de, ee >= 98%) in 13 steps and an overall yield of 5.6%. In addition, three alternative approaches toward the aglycon 3 are also described focusing on (1) the alkylation of the 2-benzazepinedithianes 35 and 36 with the electrophile 11, (2) a radical cyclization of the precursor (R/S,S,S)-39, and (3) an intramolecular arylation reaction of the aryl ketone 47.